EP0367014A2 - Ein Formgedächtnis aufweisender Hohlkörper und Verfahren zu dessen Verarbeitung - Google Patents

Ein Formgedächtnis aufweisender Hohlkörper und Verfahren zu dessen Verarbeitung Download PDF

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Publication number
EP0367014A2
EP0367014A2 EP89119214A EP89119214A EP0367014A2 EP 0367014 A2 EP0367014 A2 EP 0367014A2 EP 89119214 A EP89119214 A EP 89119214A EP 89119214 A EP89119214 A EP 89119214A EP 0367014 A2 EP0367014 A2 EP 0367014A2
Authority
EP
European Patent Office
Prior art keywords
hollow body
glass transition
transition point
deformed
shape memory
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89119214A
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English (en)
French (fr)
Other versions
EP0367014A3 (en
EP0367014B1 (de
Inventor
Makoto Nagoya Technical Inst. Mitsubishi Shimizu
Shunichi Nagoya Technical Inst. Mitsubishi Hayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Heavy Industries Ltd filed Critical Mitsubishi Heavy Industries Ltd
Publication of EP0367014A2 publication Critical patent/EP0367014A2/de
Publication of EP0367014A3 publication Critical patent/EP0367014A3/en
Application granted granted Critical
Publication of EP0367014B1 publication Critical patent/EP0367014B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/003—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2250/00—Compositions for preparing crystalline polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2280/00—Compositions for creating shape memory

Definitions

  • the present invention relates to a hollow body molded from a thermoplastic polyurethane elastomer having the shape memory function and also to a method of working the same.
  • Polyurethane having a glass transition point as low as about -40°C exhibits a low modulus even at low tempera­tures and hence can be used in the application areas for ordinary natural rubber and synthetic rubber.
  • polyurethane having a glass transition point as high as about 100-110°C exhibits a high modulus and good abrasion resistance even at high temperatures and hence finds use as a raw material for artificial wood.
  • Glass transition point will be referred to as Tg here strictlyinafter.
  • a shape memory polyurethane elastomer in Japanese Patent Laid-open No. 293214/1986. It provides a molding which takes on an as-molded shape and deformed shape when it is heated or cooled to a proper temperature. In other words, the molding takes on a deformed shape when it is deformed at a temperature lower than the molding temperature and then cooled to a temperature below Tg while being kept deformed, so that the deformation is set. The deformed molding restores its original shape when it is heated to a temperature higher than Tg and lower than the molding tem­perature.
  • the reference cited above discloses two kinds of shape memory polyurethane elastomers.
  • One is composed of an isophorone-based isocyanate, a polyol, and an adduct of trimethylol propane with tolylene diisocyanate (as a chain extender).
  • the other is composed of 2,4-tolylene diisocy­anate, a polyol, and 1,4-butanediol (as a chain extender).
  • polyurethane elastomers contain a large amount of excess NCO groups at the terminals of the polymer mole­cules so that they exhibit rubber elasticity at a tempera­ture higher than the Tg.
  • the first one has crosslinkage formed by a trifunctional chain extender.
  • Polyurethane elastomers having crosslinkage resemble a thermosetting polymer and hence are limited in the freedom of fabrication. That is, they are very difficult to process by injection molding, extrusion molding, blow molding, or the like.
  • the first aspect of the present invention resides in a shape memory hollow body which is molded from a polyure­thane elastomer produced by prepolymer process from a raw material composed of a difunctional diisocyanate, difunc­tional polyol, and difunctional chain extender containing active hydrogen in a molar ratio of 2.00-1.10 : 1.00 : 1.00-0.10, said polyurethane elastomer containing NCO groups and OH groups in almost equal amounts at the termi­nals of the polymer chains and having a glass transition point in the range of -50 to 60°C and a crystallinity of 3 to 50 wt%, said hollow body remembering its as-molded basic shape but taking on a deformed shape which is given when it is deformed at a temperature higher than the glass transition point of the polymer and lower than the molding temperature and then set when it is cooled in the deformed state to a temperature lower than the glass transition point.
  • the second aspect of the present invention resides in a method of working the above-mentioned shape memory hollow body remembering its basic shape, said method com­prising the steps of deforming the hollow body at a tem­perature higher than the glass transition point and lower than the molding temperature and then cooling it in the deformed state to a temperature lower than the glass transition point, thereby setting it in the deformed state, combining the deformed hollow body with another member, and heating the combination to a temperature higher than the glass transition point, thereby causing it to restore its basic shape and achieving firm bonding of the hollow body to the member.
  • the conventional shape memory polyurethane elastomer molding depends on rigid allophanate linkages for its rubber elasticity at a temperature higher than its Tg.
  • the allophanate linkages result from the intermolecular crosslinking which takes place when excess terminal NCO groups react with urethane linkages.
  • the shape memory polyurethane elastomer in the present inven­tion is a thermoplastic chain polymer which is composed of a difunctional isocyanate, polyol, and chain extender according to a specific formulation but contains no excess terminal NCO groups. It is characterized by a specific crystallinity, a Tg approximate to room temperature, and a specific ratio of moduli measured at temperatures above and below the Tg.
  • This polyurethane elastomer has the partial crystallization instead of the intermolecular crosslinking. Therefore, it is a thermoplastic polymer of chain structure; nevertheless, it exhibits rubber elastic­ity at a temperature higher than its Tg and takes on the as-molded shape and deformed shape at temperatures above and below its Tg. In other words, it has the shape memory function.
  • This thermoplastic polyurethane elastomer can be easily molded into a hollow body by melt molding such as injection molding and extrusion molding.
  • thermoplastic polyurethane elastomer in the present invention should preferably have a crystallinity in the range of 3 to 50 wt%. With a crystallinity lower than 3 wt%, the polymer will have a low rubber elasticity at a temperature higher than its Tg. Conversely, with a crystallinity higher than 50 wt%, the polymer will have a high rubber elasticity at a temperature higher than its Tg, with the result that the ratio of moduli at tempera­tures 10°C above and below its Tg is smaller.
  • the polyurethane polymer in the present invention is produced from the following raw materials, which are illustrative only and not limitative.
  • the first raw material is a difunctional isocyanate which is represented by the general formula OCN-R-NCO, where R is a group having no or one or two benzene rings. It includes, for example, 2,4-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, carbodiimide-modified 4,4′-diphenylmethane diisocyanate, and hexamethylene diis­ocyanate.
  • the second raw material is a difunctional polyol which is represented by the general formula OH-R′-OH, where R′ is a group having no or one or two benzene rings.
  • the second raw material may also be a reaction product of said difunctional polyol and a difunctional carboxylic acid or cyclic ether. It includes, for example, polypro­pylene glycol, 1,4-butane glycol adipate, polytetramethy­lene glycol, polyethylene glycol, and an adduct of bisphenol-A with propylene oxide.
  • the third raw material is a difunctional chain extender containing active hydrogen which is represented by the general formula OH-R ⁇ -OH, where R ⁇ is a (CH2) n group or a group having no or one or two benzene rings. It includes, for example, ethylene glycol, 1,4-butane glycol, bis(2-­hydroxyethyl)hydroquinone, an adduct of bisphenol-A with ethylene oxide, and an adduct of bisphenol-A with propy­lene oxide.
  • the thus produced polyurethane elastomer may be rep­resented by the following general formula.
  • HOR ⁇ OCONH(RNHCOOR′OCONH) n RNHCOOR ⁇ OCONH(RNHCOOR′OCONH) m ­RNHCOOR ⁇ OH where m is 1-16 and n is 0-16.
  • a prepolymer is prepared by reacting, in the absence of catalyst, an iso­cyanate component and a polyol component in the ratio shown in Table 1.
  • a chain extender in the ratio shown in Table 1.
  • the resulting mixture is heat-cured to give the shape memory polyure­thane elastomer, which has the basic physical properties as shown in Table 1.
  • Tg represents the glass transition point (°C)
  • E/E′ represents the ratio of the tensile modulus at a temperature 10°C lower than the Tg to the tensile modulus at a temperature 10°C higher than the Tg.
  • the crystallinity (wt%) was measured by X-ray diffractometry.
  • the hollow body pertaining to the present invention is made of the above-mentioned shape memory polyurethane elastomer. It remembers its basic shape when it is molded. It is given its second shape (deformed shape) when it is deformed at a temperature higher than its Tg and lower than its molding temperature and then cooled in the deformed state to a temperature lower than its Tg. Subsequently, the deformed hollow body is combined with another member, and the combination is heated to a temper­ature higher than its Tg, so that the hollow body restores its basic shape, firmly joining itself to the member.
  • a hollow body (inner pipe) made of the shape memory polyurethane elastomer was fitted into an outer pipe according to the following procedure.
  • a polymer having a Tg of 48°C was prepared by prepolymer process according to the formulation of sample No. 40 shown in Table 1.
  • the polymer was made into a cylindrical hollow body 1a having an outside diameter of 10.4 cm and a wall thickness of 5 mm by extrusion molding.
  • This cylindrical hollow body 1a was heated to about 65°C and then collapsed by pressing. It was cooled to about 40°C in the collapsed state so that it was set deformed. Thus there was obtained a collapsed hollow body 1b .
  • the collapsed hollow body 1b was inserted into a steel pipe 2 having an inside diameter of 10 cm. (The resulting combination is indicated by 3a .)
  • the collapsed hollow body 1b inserted into the steel pipe 3a was heated by blowing hot air (about 65°C), so that it restored its original cylindrical shape.
  • a composite pipe 3b composed of a steel pipe 2 and a cylindrical hollow body 1a of polyurethane elastomer which was firmly bonded to the inside of the steel pipe.
  • This example shows that the use of the shape memory function overcomes the difficulty which was encountered in the past when the inside of a small steel pipe was coated with a polyurethane elastomer.
  • a polymer having a Tg of 40°C was prepared by prepo­lymer process according to the formulation of sample No. 39 shown in Table 1.
  • the polymer was molded into a straight pipe (not shown) having an outside diameter of 5 cm and a wall thickness of 3 mm. This straight pipe remembers its as-molded shape.
  • the end 4 (3 cm long) of the pipe was heated to about 60°C and then contracted until the outside diameter was 4 cm.
  • the pipe was cooled to about 35°C, with the end contracted, so that the con­tracted shape was set. Thus there was obtained a pipe 5 as shown in Fig. 2.
  • the end 4 of the pipe 5 was inserted into a pipe 6 having an inside diameter of 4.5 cm. When they are heated to about 60°C, the end of the pipe 5 restored its original shape, joining itself firmly to the inside of the pipe 6 .
  • the above-mentioned joining procedure may be applied to joining an elbow made of shape memory polymer to a steel pipe.
  • thermoplas­tic polyurethane elastomer having the shape memory func­tion can be molded into a hollow body of any shape by melt molding such as injection molding, extrusion molding, and blowing molding.
  • the shape memory hollow body of the present invention remembers its basic shape, takes on its second shape (e.g., reduced or enlarged diameter, and bending), and restores its basic shape after it has been combined with another member. This property makes it pos­sible to join the hollow body firmly to another member.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Sink And Installation For Waste Water (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
EP89119214A 1988-10-18 1989-10-17 Ein Formgedächtnis aufweisender Hohlkörper und Verfahren zu dessen Verarbeitung Expired - Lifetime EP0367014B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP63260491A JPH066349B2 (ja) 1988-10-18 1988-10-18 形状記憶性管体及びその施工方法
JP260491/88 1988-10-18

Publications (3)

Publication Number Publication Date
EP0367014A2 true EP0367014A2 (de) 1990-05-09
EP0367014A3 EP0367014A3 (en) 1990-12-19
EP0367014B1 EP0367014B1 (de) 1995-08-02

Family

ID=17348703

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89119214A Expired - Lifetime EP0367014B1 (de) 1988-10-18 1989-10-17 Ein Formgedächtnis aufweisender Hohlkörper und Verfahren zu dessen Verarbeitung

Country Status (5)

Country Link
EP (1) EP0367014B1 (de)
JP (1) JPH066349B2 (de)
KR (1) KR920003921B1 (de)
CA (1) CA2000201C (de)
DE (1) DE68923679T2 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000013880A1 (en) * 1998-09-08 2000-03-16 Dsm N.V. Connection with a component produced of a thermoplastic elastomer
US6193699B1 (en) 1991-03-08 2001-02-27 Nissho Corporation Medical tube
EP1203038A1 (de) * 1999-07-20 2002-05-08 AorTech Biomaterials Pty Ltd Formgedächtnis- polyurethan- oder polyurethan-harnstoff-polymere
WO2002081320A1 (fr) 2001-03-22 2002-10-17 Mei Yi Zhu Dispositif de bouchage inviolable
EP1449863A1 (de) * 2001-10-31 2004-08-25 Mitsubishi Heavy Industries, Ltd. Matrixharzzusammensetzung für fasern, verstärkte kunststoffe und verfahren zur herstellung von faserverstärkten kunststoffen
EP1471089A2 (de) * 2003-03-31 2004-10-27 Mitsubishi Heavy Industries, Ltd. Prepreg für faserverstärkte Kunststoffe und Verfahren zur Herstellung
WO2005103201A1 (en) * 2004-03-31 2005-11-03 University Of Connecticut Shape memory main-chain smectic-c elastomers

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02214715A (ja) * 1989-02-16 1990-08-27 M D Kasei Kk 高分子熱可塑性ウレタンエラストマーの製造方法及び高分子熱可塑性ウレタンエラストマー成形体
JPH02215821A (ja) * 1989-02-16 1990-08-28 M D Kasei Kk 高分子熱可塑性ウレタンエラストマーの製造方法及び高分子熱可塑性ウレタンエラストマー成形体
JPH03237117A (ja) * 1990-02-15 1991-10-23 Mitsubishi Heavy Ind Ltd 高分子熱可塑性ウレタンエラストマーの製造方法及び高分子熱可塑性ウレタンエラストマー成形体
JP4242706B2 (ja) * 2003-06-03 2009-03-25 ニッタ株式会社 熱可塑性ポリウレタン成形品およびその製造方法
US7951319B2 (en) * 2006-07-28 2011-05-31 3M Innovative Properties Company Methods for changing the shape of a surface of a shape memory polymer article

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1534052A (fr) * 1967-06-15 1968-07-26 Dunlop Sa Manchons d'isolation thermique et leur fabrication
FR1549412A (de) * 1966-10-17 1968-12-13
DE1704160A1 (de) * 1968-02-17 1971-04-22 Kabel Und Metallwerke Guthoffn Verwendung von C-O- und N-H-Gruppen enthaltendem Polyurethan als Material fuer Schrumpfartikel
US3624045A (en) * 1965-10-22 1971-11-30 Raychem Corp Crosslinked heat recoverable thermoplastic polyurethanes
JPS61293214A (ja) * 1985-06-21 1986-12-24 Mitsubishi Heavy Ind Ltd 高分子エラストマ−成形体及びその使用方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58118211A (ja) * 1982-01-07 1983-07-14 Eagle Ind Co Ltd 船尾管の防食ライニング方法
JPS62138214A (ja) * 1985-12-12 1987-06-22 Nippon Petrochem Co Ltd 超高分子量ポリエチレンパイプの成形方法
JPS62129028A (ja) * 1985-11-29 1987-06-11 オリンパス光学工業株式会社 内視鏡

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3624045A (en) * 1965-10-22 1971-11-30 Raychem Corp Crosslinked heat recoverable thermoplastic polyurethanes
FR1549412A (de) * 1966-10-17 1968-12-13
FR1534052A (fr) * 1967-06-15 1968-07-26 Dunlop Sa Manchons d'isolation thermique et leur fabrication
DE1704160A1 (de) * 1968-02-17 1971-04-22 Kabel Und Metallwerke Guthoffn Verwendung von C-O- und N-H-Gruppen enthaltendem Polyurethan als Material fuer Schrumpfartikel
JPS61293214A (ja) * 1985-06-21 1986-12-24 Mitsubishi Heavy Ind Ltd 高分子エラストマ−成形体及びその使用方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 11, no. 163 (C-424)[2610], 26th May 1987; & JP-A-61 293 214 (MITSUBISHI) *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6193699B1 (en) 1991-03-08 2001-02-27 Nissho Corporation Medical tube
WO2000013880A1 (en) * 1998-09-08 2000-03-16 Dsm N.V. Connection with a component produced of a thermoplastic elastomer
NL1010022C2 (nl) * 1998-09-08 2000-04-03 Dsm Nv Verbinding met een onderdeel vervaardigd uit een thermoplastisch elastomeer.
US6878225B2 (en) 1998-09-08 2005-04-12 Dsm Ip Assets B.V. Connection with a component produced of a thermoplastic elastomer
EP1203038A1 (de) * 1999-07-20 2002-05-08 AorTech Biomaterials Pty Ltd Formgedächtnis- polyurethan- oder polyurethan-harnstoff-polymere
EP1203038A4 (de) * 1999-07-20 2002-10-30 Aortech Biomaterials Pty Ltd Formgedächtnis- polyurethan- oder polyurethan-harnstoff-polymere
WO2002081320A1 (fr) 2001-03-22 2002-10-17 Mei Yi Zhu Dispositif de bouchage inviolable
EP1449863A4 (de) * 2001-10-31 2005-01-19 Mitsubishi Heavy Ind Ltd Matrixharzzusammensetzung für fasern, verstärkte kunststoffe und verfahren zur herstellung von faserverstärkten kunststoffen
EP1449863A1 (de) * 2001-10-31 2004-08-25 Mitsubishi Heavy Industries, Ltd. Matrixharzzusammensetzung für fasern, verstärkte kunststoffe und verfahren zur herstellung von faserverstärkten kunststoffen
CN1302039C (zh) * 2001-10-31 2007-02-28 三菱重工业株式会社 纤维增强塑料用基质树脂组合物及纤维增强型塑料的制造方法
US7695588B2 (en) 2001-10-31 2010-04-13 Mitsubishi Heavy Industries, Ltd. Matrix resin composition for fiber-reinforced plastics and process for production of fiber-reinforced plastics
EP1471089A2 (de) * 2003-03-31 2004-10-27 Mitsubishi Heavy Industries, Ltd. Prepreg für faserverstärkte Kunststoffe und Verfahren zur Herstellung
EP1471089A3 (de) * 2003-03-31 2005-12-21 Mitsubishi Heavy Industries, Ltd. Prepreg für faserverstärkte Kunststoffe und Verfahren zur Herstellung
EP2151459A3 (de) * 2003-03-31 2012-04-18 Mitsubishi Heavy Industries, Ltd. Prepeg für faserverstärkte Kunststoffe und Verfahren zur Herstellung
US8945683B2 (en) 2003-03-31 2015-02-03 Mitsubishi Heavy Industries, Ltd. Prepreg for fiber reinforced plastic and production process thereof
WO2005103201A1 (en) * 2004-03-31 2005-11-03 University Of Connecticut Shape memory main-chain smectic-c elastomers
US7601274B2 (en) 2004-03-31 2009-10-13 The University Of Connecticut Shape memory main-chain smectic-C elastomers
US7799243B2 (en) 2004-03-31 2010-09-21 University Of Connecticut Shape memory main-chain smectic-C elastomers

Also Published As

Publication number Publication date
CA2000201C (en) 1996-01-16
JPH066349B2 (ja) 1994-01-26
KR920003921B1 (ko) 1992-05-18
KR900006110A (ko) 1990-05-07
JPH02107431A (ja) 1990-04-19
DE68923679D1 (de) 1995-09-07
CA2000201A1 (en) 1990-04-18
EP0367014A3 (en) 1990-12-19
EP0367014B1 (de) 1995-08-02
DE68923679T2 (de) 1996-01-18

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